JP4380990B2 - Pyridone dyes, their production process and their use in the production of colored plastic or colored polymer particles - Google Patents

Abstract

The present invention relates to pyrifone azo dyes of formula (1), wherein A is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzoisothiazole, thiadiazole, indazole, benzotriazole, pyrazole, anthraquinone, naphttholic acid imide, chromone, phthalimide or diphenylene oxide series, R<SUB>1 </SUB>is hydrogen, unsubstituted or hydroxyl- or phenyl-substituted C<SUB>1</SUB>-C<SUB>6</SUB>alkyl, it being possible for the alkyl chain to be interrupted from C<SUB>3 </SUB>upwards by one or more oxygen atoms, or has the meanings of R<SUB>2</SUB>, R<SUB>2 </SUB>is a radical of formulae (2), (3), (4), (5), (6), or (7), wherein B is a bridging member, R<SUB>4 </SUB>is alkyl or aryl, R<SUB>5 </SUB>and R<SUB>6 </SUB>are each independently of the other alkyl, aryl or heteroaryl and A is as defined for formula (1), or R<SUB>1 </SUB>and R<SUB>2 </SUB>toghether with the nitrogen atom in NR<SUB>1</SUB>R<SUB>2 </SUB>form a heterocyclic ring, Y is cyano, -CONH<SUB>2 </SUB>or CH<SUB>2</SUB>SO<SUB>3</SUB>H, and n is an integer from 2 to 6, to a process for their preparation and to their use in the production coloured plastics or polymeric color particles.

Description

  The present invention relates to pyridone azo dyes, processes for their production and their use in the production of colored plastic or colored polymer particles.

  Pyridone azo dyes and their use in dyeing semi-synthetic or synthetic hydrophobic fiber materials are known. However, when known pyridone azo dyes are used for kneading coloring of synthetic materials (plastics), such dyes do not always meet the highest requirements, especially in terms of heat resistance, dye transfer and / or dye strength. Is shown not to meet. Accordingly, there is a need for new pyridone azo dyes that provide heat-stable and dyed and strong kneaded colorants and that exhibit good overall fastness.

  Surprisingly, it has now been found that the pyridone azo dyes of the present invention meet the above criteria to a considerable extent.

  Accordingly, the present invention provides the formula (1):

[Where,
A is a group of benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzoisothiazole, thiadiazole, indazole, benzotriazole, pyrazole, anthraquinone, naphthalic imide, chromone, phthalimide or diphenylene oxide series ,
Is R ₁ hydrogen, unsubstituted or hydroxy- or phenyl-substituted C ₁ -C ₆ alkyl (which may be interrupted by one or more oxygen atoms above C ₃ for the alkyl chain)? Or has the meaning of R ₂ ,
R ₂ represents formula (2), (3), (4), (5), (6) or (7):

Wherein B is a bridge moiety, R ₄ is alkyl or aryl, R ₅ and R ₆ are each independently of the other alkyl, aryl or heteroaryl, and A is as defined for formula (1) Or R ₁ and R ₂ together with the nitrogen atom in —NR ₁ R ₂ form a heterocycle;
Y is cyano, —CONH ₂ or —CH ₂ SO ₃ H, and n is an integer of 2 to 6)
Is a group represented by
It is related with the pyridone azo dye shown by these.

A is preferably a benzene series diazo component group.
Particularly preferred as A is formula (8):

{Wherein R ₇ is hydrogen or halogen;
R ₈ is hydrogen, halogen, cyano, -CF _3, -COOR ₁₁ [wherein, R ₁₁ is the alkyl group interrupted by oxygen is also good C ₁ -C ₄ alkyl], Oh Rui benzyl or —SO ₂ R _12, where R ₁₂ is —NR ₁₃ R ₁₄ or phenyl, and R ₁₃ is hydrogen or C ₁ -C ₄ alkyl, and R ₁₄ is C ₁ -C ₄ alkyl or benzyl. )
R ₉ is hydrogen or halogen, and R ₁₀ is hydrogen or a group —SO ₂ —O—C ₆ H ₅ }
It is group shown by these.

C ₁ -C ₆ alkyl as R ₁ is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, tert-amyl (1,1-dimethylpropyl), 1,1,3,3-tetramethylbutyl, hexyl, 1-methylpentyl, neopentyl, cyclopentyl, cyclohexyl, and related isomers, and in particular methyl. R ₁ is preferably methyl, ethyl or the group —CO—R ₆ (7), and in particular hydrogen.

Alkyl in the definition of R ₄ , R ₅ and R ₆ is for example C ₁ -C ₄ alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, and C ₁ -C is ₂ alkoxy or C ₁ -C ₄ alkyl substituted with benzyloxy or cyclopentyl and C ₅ -C ₆ cycloalkyl such as cyclohexyl.

Aryl in the definition of R ₄ , R ₅ and R ₆ is, for example, phenyl or naphthyl.

The heterocyclic ring formed by the nitrogen atom of R _1, R ₂ and in -NR ₁ R ₂ is, for example, phthalimidyl, a heterocyclic lactams or saccharin series.

Heteroaryl in the definition of R ₅ is, for example, thiazolyl, triazolyl or thiadiazolyl.

Heteroaryl in the definition of R ₆ is, for example, thiophene or furan.

C ₁ -C ₄ alkyl as R ₁₁ , R ₁₃ and R ₁₄ is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
Y is preferably cyano.
Halogen as R ₇ , R ₈ and R ₉ is bromine, iodine and especially chlorine.

  Bridge part B is, for example, phenylene, naphthylene, thienyl or furyl.

  n is preferably 2 to 4, in particular 2 or 3.

  Particularly preferred are formulas (10), (11), (12), (13), (14) or (15):

It is a pyridone azo dye represented by

  The invention also relates to a process for the preparation of the azo dye of formula (1) according to the invention.

  The dye is produced, for example, as follows. Formula (50):

Is diazotized according to a conventional procedure, and then represented by the formula (51):

(A, R ₁ , R ₂ , Y and n are as defined in formula (1))
Coupling to a coupling component represented by

  The diazotization of the compound of formula (50) is carried out in a manner known per se, for example using sodium nitrite in an acidic, for example hydrochloric or sulfuric acid-containing aqueous medium. However, diazotization can also be carried out using other diazotizing agents such as nitrosylsulfuric acid. In diazotization, additional acids such as phosphoric acid, sulfuric acid, acetic acid, propionic acid, hydrochloric acid or a mixture of such acids, such as a mixture of propionic acid and acetic acid, may be present in the reaction medium. The diazotization is advantageously carried out at a temperature of -10 to 30 ° C, for example -10 ° C to room temperature.

  The coupling of the diazotized compound of formula (50) to the coupling component of formula (51) is likewise carried out in a known manner, for example in acidic medium, aqueous medium or aqueous organic medium, preferably -10-30. It is achieved at temperatures of ° C., especially below 10 ° C. Examples of acids used are hydrochloric acid, acetic acid, propionic acid, sulfuric acid or phosphoric acid.

  The compounds of formula (50) are known or can be prepared by methods known per se.

  Compounds of formula (51) are known or are known per se, for example formula (52):

First, the compound represented by formula (53):

And then the formula (54):

Is reacted with a compound of formula (55):

Or a compound of formula (52):

First, 2 mol of the compound represented by formula (56):

And then the formula (54):

Is reacted with 2 moles of the compound of formula (57):

It can manufacture by forming the compound shown by these.

  Starting from the compounds of the formulas (55) and (57), the corresponding compounds of the formula (51) are prepared in a manner known per se, for example by further reaction of benzoyl chloride or acetyl chloride with an amino group. be able to.

  Compounds of formulas (52) to (54) and (56) are known and can be prepared by methods known per se.

  The present invention also relates to a process for producing colored plastic or color polymer particles comprising mixing together a high molecular weight organic material and a dye effective amount of one or more pyridone azo dyes of formula (1).

  The coloring of the high molecular weight organic substances with the pyridone azo dyes of the formula (1) is carried out by mixing such pyridone azo dyes into these substances, for example using a roll mill, a mixing device or a grinding device, The pyridone azo dye is dissolved or finely dispersed in the high molecular weight material. The high molecular weight organic material with the mixed pyridone azo dye is then processed using processes known per se, such as calendering, compression molding, extrusion, coating, spinning, casting or injection molding, whereby the colored material is It will take the final form. The mixing of the pyridone azo dye is, for example, an extrusion molding machine in which a powdery pyridone azo dye and at the same time a granular or powdery high molecular weight organic material and optionally additional components, for example additives, are mixed just before processing. It is also possible to carry out immediately before the actual processing step by continuously feeding directly to the intake zone. However, generally, since a more uniform coloring of the substrate can be obtained, it is preferable to previously mix the pyridone azo dye with the high molecular weight material.

  It is often desirable to add so-called plasticizers to the high molecular weight compounds before molding in order to produce non-hard moldings or to reduce their brittleness. For example, esters of phosphoric acid, phthalic acid or sebacic acid can be used as plasticizers. In the process of the present invention, the plasticizer can be incorporated into the polymer before or after the colorant is incorporated. In order to achieve different shades, in addition to the pyridone azo dye of formula (1), further pyridone azo dyes or other colorants can be added in any desired amount, optionally further additives such as fillers or desiccants. At the same time, it can be added to a high molecular weight organic material.

  In order to improve the light fastness, it is advantageous to mix UV absorbers into plastic or polymer particles which are colored with the pyridone azo dyes of the formula (1) according to the invention. The amount of UV absorber can vary within wide limits and is preferably 0.01 to 1.0% by weight, in particular 0.05 to 0.6% by weight, based on the weight of the plastic or polymer particles. More particularly, 0.1 to 0.4% by weight of UV absorber is used.

  Suitable UV absorbers are in particular 2- (2′-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of substituted or unsubstituted benzoic acids, acrylates, oxamides, 2- (2-hydroxy Phenyl) -1,3,5-triazines, resorcinol monobenzoates or formamidines, and a specific weight at 25 ° C. of 1200 to 1400, preferably 1300 to 1350, formula (60):

It is a polyester UV absorber shown by these.

  Examples of 2- (2′-hydroxyphenyl) benzotriazoles include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2). '-Hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl) ) Phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5) '-Methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphene) ) Benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- ( 3 ′, 5′-bis (α, α-dimethylbenzyl) -2′-hydroxyphenyl) benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-octyloxycarbonylethyl) ) Phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2 -(3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5 Lorobenzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5) '-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl Benzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethyl Til) -6-benzotriazol-2-ylphenol]; 2- [3′-tert-butyl-5 ′-(2-methoxycarbonylethyl) -2′-hydroxyphenyl] -2H-benzotriazole and polyethylene glycol 300 Transesterification product with

Wherein R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl; 2- [2'-hydroxy-3 '-(α, α- Dimethylbenzyl) -5 '-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; and 2- [2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl) -5 '-(α, α-dimethylbenzyl) phenyl] benzotriazole.

  Examples of 2-hydroxybenzophenones include 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ′, 4′-trihydroxy and 2 ′. -Hydroxy-4,4'-dimethoxy derivatives.

  Examples of 2- (2-hydroxyphenyl) -1,3,5-triazines include 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2 -(2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) ) − , 6-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl)- 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- 2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 -Hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4 , 6-Tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl)- Examples include 6-phenyl-1,3,5-triazine.

  From oxamides, for example, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2, 2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5 -Tert-butyl-2'-ethyloxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, and o- and p-methoxy-disubstituted oxanilides Mention may be made of mixtures and mixtures of o- and p-ethoxy-disubstituted oxanilides.

  Examples of substituted or unsubstituted benzoic acid esters include 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3, 2,4-di-tert-butylphenyl 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl Examples include octadecyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

  Examples of acrylates include ethyl-α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyano-β- Methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate or N- (β-carbomethoxy-β-cyanovinyl)- 2-methylindoline is mentioned.

  Resorcinol monobenzoate is, for example, formula (61):

It is a compound shown by these.

  Formamidine is, for example, formula (62):

It is a compound shown by these.

  Coloring in the form of thermoplastics, in particular fibers, granules or moldings, for example containers for solid or liquid substances, for example bottles, is preferred. Preferred high molecular weight organic materials that are colored according to the invention are very common polymers having a dielectric constant of 2.5 or more, in particular polyester, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), Polyamide, polyethylene, polypropylene, styrene / acrylonitrile (SAN) or acrylonitrile / butadiene / styrene (ABS). Polyester and polyamide are particularly preferred. Particularly preferred are linear aromatic polyesters obtained by polycondensation of terephthalic acid or naphthalene-2,6-dicarboxylic acid and glycol, particularly ethylene glycol, or terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane. Condensates such as polyethylene terephthalate (PET), polyethylene naphthalene-2,6-dicarboxylate (PEN) or polybutylene terephthalate (PBTP); also polycarbonates such as α, α-dimethyl-4,4-dihydroxy-diphenylmethane and From phosgene or polyvinyl chloride and polyamide based polymers such as polyamide-6 or polyamide-6,6.

  The pyridone azo dyes according to the invention impart to the above mentioned materials, in particular polyester materials, a strong and homogeneous color on dyeing with very good use fastnesses, in particular good light fastness and high temperature light fastness. . Particular mention may be made of the good migration fastness and heat transfer fastness of the dyeings obtained.

  The present invention also relates to a process for producing colored plastic or color polymer particles comprising using a combination of a pyridone azo dye of formula (1) and a UV absorber, wherein the pyridone azo dye and UV absorber of formula (1) The above meanings and preferred meanings apply.

  The present invention also relates to a plastic kneaded and colored by the above method.

  The following examples illustrate the invention in detail. Unless indicated otherwise, parts are parts by weight and percentages are percentages by weight. Temperature is shown in ° C. The relationship between the weight part and the capacity part is the same as that between gram and cubic centimeter.

Example 1
(A) 140.0 ml of water was placed in a reaction vessel and cooled to 0-5 ° C. Then, over the course of 30 minutes, 405.2 ml of ethylenediamine and then 215.4 ml of ethyl cyanoacetate were added dropwise and the temperature was kept below 20 ° C. by cooling. The reaction mixture was then stirred at 20 ° C. for 16 hours, excess ethylenediamine was removed in vacuo at 60 ° C., and the mixture was stirred at 40 ° C. for 1 hour.
Next, 253.0 ml of ethyl acetoacetate was added dropwise, and the temperature was raised to 70 ° C. by the end of the addition. As soon as the ethyl acetoacetate addition was complete, 168.0 ml of 30% aqueous ammonia was added followed by 1400.0 ml of propanol and the reaction mixture was stirred at 70-75 ° C. for 16 hours. The resulting suspension was filtered, taken up in 1500.0 ml of ethanol, stirred for 14 hours at 20 ° C. and filtered again. The filter cake was washed several times with a total of 1000.0 ml of ethanol and dried.
Formula (55):

263.6 g of the compound represented by

(B) 50.0 g of the compound of formula (55) was suspended in 500.0 ml of water, heated to 60 ° C., adjusted to pH 1.0 with 32% HCl, and stirred at 60 ° C. for 3 hours. The crystalline precipitate was then removed from the reaction mass by filtration, the mother liquor was adjusted to pH 9 with 30% aqueous NaOH and 40.0 ml of benzoyl chloride was added. The reaction mixture was then stirred for 18 hours, adding HCl if necessary to keep the pH value at 9.0. Then 100.0 g NaCl was added and the fully reacted reaction mass was adjusted to pH 0.5 with 32% HCl and stirred at 0 ° C. until the product had precipitated. The precipitated reaction product was suction filtered and dried.
Formula (58):

93.5 g of a product containing 62.3 g of the compound represented by

(C) 10.6 ml of ethyl anthranilate was placed in 110.0 ml of 98% acetic acid at 15-20 ° C. and 22.0 g of 32% HCl was added. Then 17.8 ml of 4N NaNO ₂ was added dropwise to the reaction mass and stirring was carried out at 10-15 ° C. for 1 hour. The excess nitrite was then decomposed with sulfamic acid.

(D) 14.9 g of the compound of formula (58) prepared by (B) was placed in 150.0 ml of water, 22.0 g of 30% aqueous NaOH was added, and the mixture was heated to 50 ° C. Next, 120 g of the diazo solution produced by (B) was added dropwise to the resulting suspension while adding about 200.0 g of ice and maintaining the temperature at 15 ° C. After the addition was complete, the pH value was adjusted to 5.0 and the reaction mass was stirred for 16 hours.
Thereafter, 300.0 ml of water were added and the completely reacted reaction mass was heated to 70 ° C., suction filtered, washed with water and dried.
Formula (12):

20.0 g of the pyridone azo dye represented by ## STR5 ## were obtained, which colored the polyester in a yellow shade.

Example 2
(A) 111.95 ml of diethylenetriamine was placed in the reaction flask and 236.95 ml of ethyl cyanoacetate was added at 20 ° C. and the temperature rose to about 75 ° C. The reaction mixture was stirred for 30 minutes, then 1000.0 ml of 94% ethanol was added and the mixture was stirred at 72 ° C. (reflux) for 2 hours. Thereafter, 278.3 ml of ethyl acetoacetate, 168.0 ml of 30% aqueous ammonia solution and 3000.0 ml of 94% ethanol were successively added, and the mixture was further stirred for 41 hours under reflux.
The resulting suspension is suction filtered at 75 ° C. and then washed several times with a total of 500.0 ml of 94% ethanol, after which 2000.0 ml of 94% ethanol are added and the mixture is stirred at 20 ° C. for 14 hours. . The suspension was then suction filtered and the filter cake was washed several times with a total of 1000.0 ml of 94% ethanol and dried under reduced pressure.
Formula (57):

235.6 g of a compound represented by

(B) 92.35 g of the compound of formula (57) is suspended in 1000.0 ml of water, the suspension is heated to 60 ° C., adjusted to pH 1.0 with 32% HCl and stirred at 60 ° C. for 3 hours. did. The crystalline precipitate was then removed from the reaction mass by filtration, the mother liquor was adjusted to pH 9 with 30% aqueous NaOH and 40.0 ml of benzoyl chloride was added. The reaction mixture was then stirred for 18 hours, adding HCl if necessary to keep the pH value at 9.0. Then 200.0 g NaCl was added and the fully reacted reaction mass was adjusted to pH 0.5 with 32% HCl and stirred at 0 ° C. until the product had precipitated. The precipitated reaction product was suction filtered and dried.
Formula (59):

90.0 g of the compound represented by

(C) 1.65 g of ethyl anthranilate was placed in 10.0 ml of glacial acetic acid at 15-30 ° C., 0.6 ml of 96% sulfuric acid was added and the mixture was stirred for 30 minutes. Then 1.85 ml of 40% nitrosylsulfuric acid was added dropwise to the reaction mass over 10 minutes and the mixture was stirred at 17-20 ° C. for 1 hour.

(D) 100.0 ml of dimethylformamide (DMF) was taken as a raw material, and 2.4 g of the compound of formula (59) and 10.0 ml of ice water were added with stirring. Thereafter, over the course of 30 minutes, 22.0 ml of 10% NaOH aqueous solution was added dropwise at a temperature of 5 to 10 ° C., and at the same time, in order to keep the pH value at 3 to 4 at a temperature of 3 to 4.
The reaction mixture was stirred at 0-5 ° C. for 4 hours, then adjusted to pH 4.6 and stirred at 20 ° C. for an additional 17 hours. The resulting suspension was filtered with suction, washed successively with 25.0 ml of 80% DMF, ethanol and water until the pH was greater than 6 and dried.
Formula (10):

3.3 g of a pyridone azo dye of the formula was obtained, which dyed the polyester in a yellow shade.

Examples 3-185
In a manner similar to that described in Examples 1 and 2, it is also possible to produce the following dyes listed in Tables 1-16, which also dyed the polyester in a yellow shade.

Dyeing example 1
1200.00 g of polyester particles (PET Arnite D04-300, DSM) are pre-dried at 130 ° C. for 4 hours, then 0.24 g of pyridone azo dye of formula (14) and 15 in a “roller rack” mixing device. Mix uniformly for 60 minutes at 60 revolutions per minute. The homogeneous mixture is extruded in a 6-zone extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) at a maximum temperature of 275 ° C., cooled with water and granulated (MAPAG AG, CH-3001 Granulated with Turb Etuve TE 25) from Bern and then dried at 130 ° C. for 4 hours.
The yellow polyester grains obtained had good overall fastness, in particular very good light fastness and high temperature light fastness.

Dyeing example 2
1200.00 g of polyester particles (PET Arnite D04-300, DSM) are pre-dried at 75 ° C. for 4 hours, then 0.60 g of pyridone azo dye of formula (14) and formula (63):

Was uniformly mixed at 60 revolutions per minute for 15 minutes in a “roller rack” mixing device. The homogeneous mixture is extruded in a 6-zone extruder (twin screw 25 mm from Collin, D-85560 Ebersberg) at a maximum temperature of 275 ° C., cooled with water and granulated (MAPAG AG, CH-3001 Granulated with Turb Etuve TE 25) from Bern and then dried at 130 ° C. for 4 hours.
The yellow polyester grains obtained had good overall fastness, in particular very good light fastness and high temperature light fastness.

Claims (6)

Formula (1) or (10) :

[Where,
A is the formula (8):

{Wherein R ₇ is hydrogen or halogen;
R ₈ is halogen, cyano, —CF ₃ , —COOR ₁₁ [wherein R ₁₁ is C ₁ -C ₄ alkyl optionally substituted with oxygen] or benzyl or —SO ₂ R ₁₂ Where R ₁₂ is —NR ₁₃ R ₁₄ or phenyl, and R ₁₃ is hydrogen or C ₁ -C ₄ alkyl and R ₁₄ is C ₁ -C ₄ alkyl or benzyl.
R ₉ is hydrogen or halogen, and R ₁₀ is hydrogen or a group —SO ₂ —O—C ₆ H ₅ }
The basis of
R ₁ is hydrogen, unsubstituted or hydroxy- or phenyl-substituted C ₁ -C ₆ alkyl (which may be interrupted by one or more oxygen atoms above C ₃ for the alkyl chain). Or has the meaning of R ₂ ,
R ₂ represents the formula ( 3) or (4 ):

Wherein B is a bridge moiety selected from the group consisting of phenylene, naphthalene, thienyl and furyl, R ₄ is alkyl or aryl, and R ₅ and R ₆ are each independently alkyl, aryl Or is heteroaryl, and A is as defined in formula (1), or R ₁ and R ₂ together with the nitrogen atom in —NR ₁ R ₂ form a heterocycle, Y is cyano , —CONH ₂ or —CH ₂ SO ₃ H, and n is an integer of 2 to 6.
A pyridone azo dye represented by Formula (50):

Is diazotized according to a conventional procedure, and then represented by the formula (51):

(A, R ₁ , R ₂ , Y and n are as defined in formula (1))
A method for producing a pyridone azo dye of formula (1) according to claim 1, wherein the coupling component is coupled to the coupling component represented by formula (1). A process for producing colored plastic or color polymer particles comprising admixing one or more pyridone azo dyes of formula (1) according to claim 1 with the material of the colored plastic or color polymer particles.   A process for producing colored plastic or color polymer particles comprising using a combination of a pyridone azo dye of formula (1) according to claim 1 and a UV absorber.   Use of a pyridone azo dye according to claim 1 in the production of colored plastic or colored polymer particles. Plastic or color polymer particles according to any of claims 3 or 4 .